TWI609232B - Binary photomask blank, preparation thereof, and preparation of binary photomask - Google Patents
Binary photomask blank, preparation thereof, and preparation of binary photomask Download PDFInfo
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- TWI609232B TWI609232B TW104122539A TW104122539A TWI609232B TW I609232 B TWI609232 B TW I609232B TW 104122539 A TW104122539 A TW 104122539A TW 104122539 A TW104122539 A TW 104122539A TW I609232 B TWI609232 B TW I609232B
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 152
- 239000010410 layer Substances 0.000 claims description 96
- 229910052723 transition metal Inorganic materials 0.000 claims description 92
- 150000003624 transition metals Chemical class 0.000 claims description 92
- 229910052757 nitrogen Inorganic materials 0.000 claims description 77
- 239000000758 substrate Substances 0.000 claims description 48
- 238000005530 etching Methods 0.000 claims description 41
- 230000003287 optical effect Effects 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 30
- 239000002356 single layer Substances 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- 239000010955 niobium Substances 0.000 claims description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 304
- 239000007789 gas Substances 0.000 description 20
- 238000012545 processing Methods 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 238000004544 sputter deposition Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 8
- 229910052707 ruthenium Inorganic materials 0.000 description 8
- 238000001312 dry etching Methods 0.000 description 7
- 229910052727 yttrium Inorganic materials 0.000 description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001459 lithography Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 150000001845 chromium compounds Chemical class 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 238000000206 photolithography Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 229910016006 MoSi Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000010363 phase shift Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
- G03F1/46—Antireflective coatings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/54—Absorbers, e.g. of opaque materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/54—Absorbers, e.g. of opaque materials
- G03F1/58—Absorbers, e.g. of opaque materials having two or more different absorber layers, e.g. stacked multilayer absorbers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/60—Substrates
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/66—Containers specially adapted for masks, mask blanks or pellicles; Preparation thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/80—Etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
Description
本發明係有關於一種作為半導體積體電路、CCD(電荷耦合元件)、LCD(液晶顯示元件)用彩色濾光片、磁頭等的微細加工所使用之二元光罩的素材的二元光罩坯料，尤其係有關於一種ArF準分子雷射曝光所使用之二元光罩用之二元光罩坯料、其製造方法、及使用二元光罩坯料之二元光罩的製造方法。 The present invention relates to a binary mask which is a material of a binary photomask used for microfabrication of a semiconductor integrated circuit, a CCD (Charge Coupled Device), a color filter for an LCD (Liquid Crystal Display Element), a magnetic head, or the like. The blank, in particular, relates to a binary mask blank for a binary mask used for laser exposure of ArF excimer, a method of manufacturing the same, and a method of manufacturing a binary mask using a binary mask blank.
近年來，在半導體加工中，尤其是，隨著大規模積體電路的高積體化，電路圖案的微細化愈來愈重要，對構成電路之配線圖案的細線化、或構成單元之層間的配線用之接觸孔圖案的微細化技術的要求也愈來愈高。因此，在形成此等配線圖案或接觸孔圖案的光微影術中所使用之寫入電路圖案的光罩的製造中，也隨著前述微細化，要求可更微細且正確地寫入電路圖案的技術。 In recent years, in semiconductor processing, in particular, with the high integration of large-scale integrated circuits, the miniaturization of circuit patterns has become more and more important, and the wiring patterns constituting the circuits have been thinned, or between layers of constituent units. The requirements for the miniaturization technology of the contact hole pattern for wiring are also increasing. Therefore, in the manufacture of a photomask for writing a circuit pattern used in photolithography for forming such a wiring pattern or a contact hole pattern, it is required to write the circuit pattern more finely and accurately as the miniaturization is performed. technology.
為了將精度更高的光罩圖案形成於光罩基板上，首先，必需在光罩坯料上形成高精度的阻劑圖案。實 際之對半導體基板加工時的光微影術，為了進行縮小投影，光罩圖案為實際所需之圖案尺寸的4倍左右大小，但僅此並無法緩和精度，反而，作為原版的光罩係要求比曝光後之圖案精度所要求者更高的精度。 In order to form a mask pattern having higher precision on the photomask substrate, first, it is necessary to form a high-precision resist pattern on the mask blank. real In the case of photolithography for semiconductor substrate processing, in order to reduce the projection, the mask pattern is about four times the size of the actual required pattern. However, the accuracy cannot be alleviated, but the original mask is used. Requires higher precision than required for pattern accuracy after exposure.
再者，在現行的微影術中，所欲描繪之電路圖案的尺寸係遠低於使用之光的波長，如使用將電路的形狀直接放大4倍的光罩圖案，則會因進行實際之光微影術所產生的光的干涉等的影響，無法對阻劑膜轉印仿照光罩圖案之形狀。因此，為了減少此等的影響，光罩圖案有時需予以加工成比實際之電路圖案更複雜的形狀(應用所稱OPC：Optical Proximity Correction(光學鄰近修正)等的形狀)。因此，在用以獲得光罩圖案的微影技術中，目前亦要求更高精度的加工方法。就微影性能而言，有時會以極限解析度表現之，惟就解析極限而言，光罩加工步驟的微影技術要求與使用光罩之半導體加工步驟中所使用的光微影術所需之解析極限同等程度、或較其為高的極限解析精度。 Furthermore, in current lithography, the size of the circuit pattern to be depicted is much lower than the wavelength of the light used. For example, if a reticle pattern that directly enlarges the shape of the circuit by 4 times is used, the actual light is The influence of the interference of light generated by the lithography, etc., cannot transfer the shape of the mask pattern to the resist film. Therefore, in order to reduce such effects, the mask pattern sometimes needs to be processed into a shape more complicated than the actual circuit pattern (applying a shape such as OPC: Optical Proximity Correction). Therefore, in the lithography technique for obtaining a reticle pattern, a more precise processing method is currently required. In terms of lithography performance, it is sometimes expressed in extreme resolution, but in terms of resolution limits, the lithography technique of the reticle processing step requires photolithography used in the semiconductor processing step using a reticle. The resolution limit required is equal to or higher than the limit analysis accuracy.
在光罩圖案的形成中，通常係於在透明基板上具有遮光膜的光罩坯料上形成光阻膜，進行採用電子束的圖案描繪，再經過顯像而得到阻劑圖案，其後，以所得阻劑圖案為蝕刻遮罩，對遮光膜進行蝕刻而予以加工成遮光圖案；惟，將遮光圖案微細化時，如欲在將阻劑膜的膜厚維持於與微細化前相同的狀態下進行加工，則膜厚對圖案的比，即所謂的縱橫比會變大，致阻劑的圖案形狀劣化 而無法順利地進行圖案轉印、或隨情況不同阻劑圖案發生倒塌或剝落。因此，隨著微細化，有減薄阻劑膜厚之必要。 In the formation of the mask pattern, a photoresist film is usually formed on a mask blank having a light-shielding film on a transparent substrate, patterned by an electron beam, and then developed to obtain a resist pattern, and thereafter, The obtained resist pattern is an etching mask, and the light-shielding film is etched and processed into a light-shielding pattern. However, when the light-shielding pattern is made fine, the film thickness of the resist film is maintained in the same state as before the miniaturization. When the processing is performed, the ratio of the film thickness to the pattern, that is, the so-called aspect ratio becomes large, and the pattern shape of the resisting agent is deteriorated. However, the pattern transfer cannot be smoothly performed, or the resist pattern may collapse or peel off depending on the situation. Therefore, with the miniaturization, it is necessary to reduce the thickness of the resist film.
另一方面，關於以阻劑為蝕刻遮罩進行蝕刻的遮光膜材料，迄今已提出有多種，而吾人對於蝕刻的知識見解繁多，作為標準加工步驟已然確立，因此，實用上，經常使用鉻化合物膜。就此而言，例如，作為以鉻化合物構成ArF準分子雷射曝光用之光罩坯料所需的遮光膜者，例如，日本特開2003-195479號公報(專利文獻1)中報導一種膜厚50~77nm的鉻化合物膜。 On the other hand, there have been many types of light-shielding film materials which are etched with a resist as an etching mask, and our knowledge of etching has been extensively recognized as a standard processing step. Therefore, practically, chromium compounds are often used. membrane. In this regard, for example, as a light-shielding film which is required to form a mask blank for an ArF excimer laser exposure, a film thickness of 50 is reported in Japanese Laid-Open Patent Publication No. 2003-195479 (Patent Document 1). ~77nm chromium compound film.
然而，作為鉻化合物膜等鉻系膜的一般的乾式蝕刻條件之含氧的氯系乾式蝕刻，對於有機膜亦具有一定程度進行蝕刻的性質。因此，為了進行更微細之圖案的轉印，由於前述之必要性，而以更薄的阻劑膜進行蝕刻時，於蝕刻中阻劑膜會受損，而不易正確地轉印阻劑圖案。於此，為了達成微細化與高精度之兼有，需由僅依存於阻劑性能之提升的方法，對如提升遮光膜之加工性的遮光膜材料再次進行研究。 However, the oxygen-containing chlorine-based dry etching which is a general dry etching condition of a chromium-based film such as a chromium compound film has a property of etching to some extent on the organic film. Therefore, in order to perform transfer of a finer pattern, when the etching is performed with a thinner resist film due to the necessity described above, the resist film is damaged during etching, and the resist pattern is not easily transferred. Here, in order to achieve both miniaturization and high precision, it is necessary to study the light-shielding film material which improves the workability of the light-shielding film only by the method which improves the performance of a resisting agent only.
舉例來說，日本特開2006-78807號公報(專利文獻2)示出，透過使用構成遮光膜的層的至少1層包含矽與過渡金屬作為主成分，且矽與過渡金屬的原子比為矽：金屬=4~15：1的材料，可獲得遮光性能與加工性優良的ArF準分子雷射曝光用之遮光膜。又，為了使用包含矽與過渡金屬的遮光膜來獲得更高精度的加工性，日本特 開2007-241060號公報(專利文獻3)中示出一種將以鉻系材料形成的薄膜作為硬遮罩膜使用的方法。 For example, Japanese Laid-Open Patent Publication No. 2006-78807 (Patent Document 2) discloses that at least one layer of a layer constituting a light shielding film contains ruthenium and a transition metal as main components, and an atomic ratio of ruthenium to transition metal is 矽. : A metal = 4 to 15:1 material, which provides a light-shielding film for ArF excimer laser exposure with excellent light-shielding properties and processability. Moreover, in order to obtain a higher precision processability by using a light-shielding film containing tantalum and a transition metal, Japanese Laid-Open Patent Publication No. 2007-241060 (Patent Document 3) discloses a method of using a film formed of a chromium-based material as a hard mask film.
[專利文獻1]日本特開2003-195479號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-195479
[專利文獻2]日本特開2006-78807號公報 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2006-78807
[專利文獻3]日本特開2007-241060號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-241060
[專利文獻4]日本特開平7-140635號公報 [Patent Document 4] Japanese Patent Laid-Open No. 7-140635
諸如前述，為了正確地製作更微細的圖案，則需要一種在加工時可對阻劑圖案，以不會進一步造成損傷的加工條件進行加工的遮光膜；惟，若為日本特開2007-241060號公報(專利文獻3)所提案之具備：使用含有過渡金屬與矽作為賦予穿透率降低機能的元素，且進一步視需求包含氮或氧等低原子量成分的材料的遮光膜、及鉻系之硬遮罩膜的光罩坯料時，作為有效用於縮小對阻劑之負荷的方策，可舉出與硬遮罩膜的膜厚共同減薄遮光膜之膜厚本身的方法。此時，尤其是對於遮光膜側，為了以薄膜獲得高遮光性，添加於使用之材料的氮或氧等低原子量成分便極力調成低濃度，而將所謂的金屬性較高的膜作為遮光膜使用。 For example, in order to correctly produce a finer pattern, a light-shielding film which can process a resist pattern during processing without further damage is required; however, if it is No. 2007-241060 In the publication (Patent Document 3), a light-shielding film containing a transition metal and ruthenium as an element for imparting a function of lowering the transmittance, and further containing a low atomic weight component such as nitrogen or oxygen, and a hard chrome-based material are used. In the case of the mask blank of the mask film, as a method for effectively reducing the load on the resist, a method of reducing the film thickness of the light-shielding film together with the film thickness of the hard mask film can be mentioned. In this case, in particular, on the side of the light-shielding film, in order to obtain high light-shielding property of the film, a low-atom component such as nitrogen or oxygen added to the material to be used is adjusted to a low concentration as much as possible, and a so-called film having a high metallicity is used as a light-shielding. Membrane use.
又，諸如前述，設於用以製造光罩之光罩坯料的光學機能膜，例如遮光膜或相位偏移膜等需滿足作成光罩時所需之物理特性，尤為光學特性、或化學穩定性，而為了更容易地獲得高精度的遮罩圖案，亦需提高被加工性。尤其是，隨著光微影術之目標圖案的微細化持續進展，對於遮罩圖案，亦要求更微細且更高精度的圖案。 Further, as described above, an optical functional film provided in a mask blank for manufacturing a photomask, such as a light shielding film or a phase shift film, is required to satisfy physical properties required for forming a photomask, particularly optical characteristics or chemical stability. In order to more easily obtain a high-precision mask pattern, it is also necessary to improve the workability. In particular, as the miniaturization of the target pattern of photolithography continues to progress, a finer and more precise pattern is also required for the mask pattern.
此外，由無機材料膜形成微細且高精度的圖案時，作為被加工膜之無機材料膜的膜厚較佳在滿足所需之物理特性的範圍盡可能地薄。其原因在於，諸如前述，為了將加工時所使用的阻劑圖案作成更高精度，而需將阻劑膜的膜厚做得較薄，使用由此阻劑膜所得之阻劑圖案並藉由乾式蝕刻等方法對無機材料膜進行圖案轉印之際，透過盡量減少阻劑膜的負擔，則可實施高精度的圖案轉印。 Further, when a fine and highly precise pattern is formed from the inorganic material film, the film thickness of the inorganic material film as the film to be processed is preferably as thin as possible within a range satisfying desired physical properties. The reason for this is that, as described above, in order to make the resist pattern used in the process to be more precise, it is necessary to make the film thickness of the resist film thin, and the resist pattern obtained by the resist film is used by When the inorganic material film is subjected to pattern transfer by a method such as dry etching, high-precision pattern transfer can be performed by reducing the burden of the resist film as much as possible.
尤其是，在可因應線寬為60nm以下之曝光圖案的形成的光罩用之光罩坯料中，於光罩製造時，尤其在清洗步驟等當中，為了減少遮光膜的圖案倒塌，而需減薄遮光膜的膜厚。又，為了降低光罩上之圖案設計時的三維效果，亦要求遮光膜的薄型化。 In particular, in a mask blank for a mask that can be formed in response to an exposure pattern having a line width of 60 nm or less, in order to reduce the pattern collapse of the light shielding film during the manufacture of the mask, particularly in the cleaning step, etc., it is necessary to reduce The film thickness of the thin light-shielding film. Further, in order to reduce the three-dimensional effect at the time of pattern design on the photomask, the thickness of the light shielding film is also required to be reduced.
日本特開2007-241060號公報(專利文獻3)所示之含有過渡金屬與矽作為穿透率降低機能的元素之化合物所製成的遮光膜，其對波長為200nm以下的光的遮蔽性能較高，而且能以氟系之乾式蝕刻條件進行蝕刻加工，因此，相對於微影術時用作阻劑材料的有機材料，可確保較佳的蝕刻比。然，使用此種材料時，在維持遮光性 能的狀態下予以薄膜化，對於確保加工精度方面亦屬有效，例如，欲獲得精度較高的二元光罩時，較佳為進一步減薄遮光膜的膜厚。為將遮光膜薄型化並獲得充分的遮光性能，且為了增加膜對曝光時的光的吸收係數，則需降低氮或氧等輕元素的含有率，而製成金屬性更高的膜。 A light-shielding film made of a compound containing a transition metal and ruthenium as an element having a function of lowering the transmittance as shown in JP-A-2007-241060 (Patent Document 3), which has a light shielding property against light having a wavelength of 200 nm or less. It is high and can be etched under fluorine-based dry etching conditions. Therefore, a better etching ratio can be secured with respect to an organic material used as a resist material in lithography. However, when using this material, the opacity is maintained. It is also effective in securing the processing accuracy in a state where the film can be formed in a flexible state. For example, in order to obtain a binary mask having high precision, it is preferable to further reduce the film thickness of the light shielding film. In order to reduce the thickness of the light-shielding film and obtain sufficient light-shielding performance, and to increase the absorption coefficient of light by the film during exposure, it is necessary to reduce the content of light elements such as nitrogen or oxygen to form a film having higher metallity.
本發明係為了解決前述課題而完成者，茲以提供一種可確保作為遮光膜所需之遮光性，且具備更薄之遮光膜的二元光罩坯料、其製造方法、及使用二元光罩坯料之二元光罩的製造方法為目的。 In order to solve the above problems, the present invention provides a binary mask blank which can provide a light-shielding property required for a light-shielding film and has a thinner light-shielding film, a method for producing the same, and a binary mask. A method of manufacturing a binary mask of a blank is for the purpose.
本案發明人等為解決前述課題而致力重複多次研究的結果發現，在透明基板上具備含有過渡金屬及矽或過渡金屬、矽及氮之光學濃度3.0以上的遮光膜的二元光罩坯料中，對於既定的厚度以下之遮光膜，藉由將遮光膜，以過渡金屬M、矽Si及氮N的組成滿足既定算式的單層或包含滿足既定算式的層的複數層構成，具體而言，以由(A)使遮光膜的膜厚成為47nm以下，且過渡金屬、矽及氮的組成滿足式(1)B≦0.68×A+0.23 (1) In order to solve the above-mentioned problems, the inventors of the present invention have made a lot of research and have found that a transparent mask has a light-shielding film containing a light-shielding film having a transition metal, a ruthenium or a transition metal, ruthenium and nitrogen at an optical density of 3.0 or more. For a light-shielding film having a predetermined thickness or less, a light-shielding film is composed of a single layer satisfying a predetermined formula of a transition metal M, 矽Si, and nitrogen N or a plurality of layers including a layer satisfying a predetermined formula, specifically, The film thickness of the light-shielding film is 47 nm or less by (A), and the composition of the transition metal, cerium, and nitrogen satisfies the formula (1) B ≦ 0.68 × A + 0.23 (1)
(式中，A為M相對於Si之原子比，B為N相對於 Si之原子比)的層、 (B)使遮光膜的膜厚成為43nm以下，且過渡金屬、矽及氮的組成滿足式(2)B≦1.19×A-0.19 (2) (wherein A is the atomic ratio of M to Si, and B is N relative to The atomic ratio of Si) (B) The film thickness of the light shielding film is 43 nm or less, and the composition of the transition metal, cerium, and nitrogen satisfies the formula (2) B ≦ 1.19 × A - 0.19 (2)
(式中，A、B係與式(1)相同)的層、或(C)使遮光膜的膜厚成為41nm以下，且過渡金屬、矽及氮的組成滿足式(3)B≦2.12×A-0.70 (3) (wherein A and B are the same as in the formula (1)) or (C) the film thickness of the light shielding film is 41 nm or less, and the composition of the transition metal, cerium, and nitrogen satisfies the formula (3) B ≦ 2.12 × A-0.70 (3)
(式中，A、B係與式(1)相同)的層所形成的單層或包含滿足前述式的層的複數層構成，即形成可確保作為遮光膜所需之遮光性，且具備更薄之遮光膜的二元光罩坯料，進而，藉由將前述式應用於構成元素之組成的設計，可配合膜厚有效地設計為了獲得更薄之遮光膜所需的構成元素，尤為過渡金屬、矽及氮的組成，終至完成本發明。 A single layer formed of a layer of the formula (A, B is the same as the formula (1)) or a plurality of layers including a layer satisfying the above formula, that is, a light-shielding property required to secure a light-shielding film is formed, and The binary mask blank of the thin light-shielding film, and further, by applying the above formula to the design of the constituent elements, the constituent elements required for obtaining a thinner light-shielding film can be effectively designed in combination with the film thickness, especially a transition metal The composition of hydrazine, hydrazine and nitrogen is completed until the present invention is completed.
從而，本發明係提供以下之二元光罩坯料、二元光罩坯料的製造方法、及二元光罩的製造方法。 Accordingly, the present invention provides the following binary mask blank, method of manufacturing a binary mask blank, and method of manufacturing a binary mask.
請求項1： Request item 1:
一種二元光罩坯料，其係在透明基板上具備含有過渡金屬M及矽Si或過渡金屬M、矽Si及氮N作為主成分，且由單層或複數層構成之光學濃度3.0以上的遮光膜的二元光罩坯料，其特徵為：前述遮光膜係包含過渡金屬、矽及氮的組成滿足式(1)B≦0.68×A+0.23 (1) A binary mask blank comprising a transparent substrate comprising a transition metal M and 矽Si or a transition metal M, 矽Si, and nitrogen N as main components, and having a single layer or a plurality of layers and having an optical density of 3.0 or more A binary mask blank of a film, characterized in that: the light-shielding film comprising a transition metal, niobium and nitrogen has a composition satisfying the formula (1) B ≦ 0.68 × A + 0.23 (1)
(式中，A為M相對於Si之原子比，B為N相對於Si之原子比)的層，前述遮光膜的膜厚為47nm以下。 (wherein, A is a ratio of atomic ratio of M to Si, and B is an atomic ratio of N to Si), and the thickness of the light-shielding film is 47 nm or less.
請求項2： Request 2:
一種二元光罩坯料，其係在透明基板上具備含有過渡金屬M及矽Si或過渡金屬M、矽Si及氮N作為主成分，且由單層或複數層構成之光學濃度3.0以上的遮光膜的二元光罩坯料，其特徵為：前述遮光膜係包含過渡金屬、矽及氮的組成滿足式(2)B≦1.19×A-0.19 (2) A binary mask blank comprising a transparent substrate comprising a transition metal M and 矽Si or a transition metal M, 矽Si, and nitrogen N as main components, and having a single layer or a plurality of layers and having an optical density of 3.0 or more A binary mask blank of a film, characterized in that the light-shielding film comprises a transition metal, a ruthenium and a nitrogen composition satisfying the formula (2) B ≦ 1.19 × A - 0.19 (2)
(式中，A為M相對於Si之原子比，B為N相對於Si之原子比) 的層，前述遮光膜的膜厚為43nm以下。 (wherein A is the atomic ratio of M to Si, and B is the atomic ratio of N to Si) In the layer, the film thickness of the light shielding film is 43 nm or less.
請求項3： Request item 3:
一種二元光罩坯料，其係在透明基板上具備含有過渡金屬M及矽Si或過渡金屬M、矽Si及氮N作為主成分，且由單層或複數層構成之光學濃度3.0以上的遮光膜的二元光罩坯料，其特徵為：前述遮光膜係包含過渡金屬、矽及氮的組成滿足式(3)B≦2.12×A-0.70 (3) A binary mask blank comprising a transparent substrate comprising a transition metal M and 矽Si or a transition metal M, 矽Si, and nitrogen N as main components, and having a single layer or a plurality of layers and having an optical density of 3.0 or more A binary mask blank of a film, characterized in that: the light-shielding film comprises a transition metal, niobium and nitrogen, and the composition satisfies the formula (3) B ≦ 2.12 × A - 0.70 (3)
(式中，A為M相對於Si之原子比，B為N相對於Si之原子比)的層，前述遮光膜的膜厚為41nm以下。 (wherein, A is a ratio of atomic ratio of M to Si, and B is an atomic ratio of N to Si), and the thickness of the light-shielding film is 41 nm or less.
請求項4： Request item 4:
如請求項1至3中任一項之二元光罩坯料，其中前述過渡金屬為鉬。 The binary mask blank of any one of claims 1 to 3, wherein the transition metal is molybdenum.
請求項5： Request 5:
如請求項1至3中任一項之二元光罩坯料，其中在前述遮光膜上，具有以對該遮光膜進行蝕刻時具蝕刻耐性之材料所形成的硬遮罩膜。 The binary mask blank according to any one of claims 1 to 3, wherein the light-shielding film has a hard mask film formed of a material having etching resistance when the light-shielding film is etched.
請求項6： Request item 6:
如請求項5之二元光罩坯料，其中前述過渡金屬為鉬，前述硬遮罩膜係包含鉻。 A binary mask blank according to claim 5, wherein said transition metal is molybdenum, and said hard mask film comprises chromium.
請求項7： Request 7:
一種二元光罩的製造方法，其係由二元光罩坯料製造二元光罩的方法，其特徵為包括：在如請求項1至4之二元光罩坯料的遮光膜上形成膜厚150nm以下之阻劑膜的步驟；形成該阻劑膜之蝕刻遮罩圖案的步驟；使用該阻劑膜之蝕刻遮罩圖案，對遮光膜形成光罩圖案的步驟；及去除前述阻劑膜之蝕刻遮罩圖案的步驟。 A method of manufacturing a binary mask, which is a method of manufacturing a binary mask from a binary mask blank, characterized by comprising: forming a film thickness on a light shielding film of a binary mask blank according to claims 1 to 4. a step of forming a resist film of 150 nm or less; a step of forming an etch mask pattern of the resist film; a step of forming a mask pattern on the light shielding film by etching the mask pattern of the resist film; and removing the resist film The step of etching the mask pattern.
請求項8： Request 8:
一種二元光罩的製造方法，其係由二元光罩坯料製造二元光罩的方法，其特徵為包括：在如請求項5或6之二元光罩坯料的硬遮罩膜上形成膜厚150nm以下之阻劑膜的步驟；形成該阻劑膜之蝕刻遮罩圖案的步驟；使用該阻劑膜之蝕刻遮罩圖案，對硬遮罩膜形成蝕刻遮罩圖案的步驟；使用該硬遮罩膜之蝕刻遮罩圖案，對遮光膜形成光罩圖案的步驟；及去除前述阻劑膜之蝕刻遮罩圖案及硬遮罩膜之蝕刻遮罩圖案的步驟。 A method of manufacturing a binary mask, which is a method of manufacturing a binary mask from a binary mask blank, comprising: forming on a hard mask film of a binary mask blank according to claim 5 or 6. a step of forming a resist film having a film thickness of 150 nm or less; a step of forming an etching mask pattern of the resist film; and a step of forming an etching mask pattern on the hard mask film by using the etching mask pattern of the resist film; a step of etching the mask pattern of the hard mask film, forming a mask pattern on the light shielding film; and removing the etching mask pattern of the resist film and the etching mask pattern of the hard mask film.
請求項9： Request 9:
一種二元光罩坯料的製造方法，其係製造在透明基板上具備含有過渡金屬M及矽Si或過渡金屬M、矽Si及氮 N作為主成分，且由單層或複數層構成之光學濃度3.0以上的遮光膜的二元光罩坯料之方法，其特徵為：將前述遮光膜形成為包含過渡金屬、矽及氮的組成滿足式(1)B≦0.68×A+0.23 (1) A method for manufacturing a binary mask blank, which is provided on a transparent substrate and comprises a transition metal M and 矽Si or transition metal M, 矽Si and nitrogen A method of using N as a main component and a binary mask blank of a light-shielding film having an optical density of 3.0 or more, which is composed of a single layer or a plurality of layers, characterized in that the light-shielding film is formed to have a composition containing a transition metal, niobium, and nitrogen. Equation (1)B≦0.68×A+0.23 (1)
(式中，A為M相對於Si之原子比，B為N相對於Si之原子比)的層，將遮光膜的膜厚形成為47nm以下。 (wherein, A is a ratio of atomic ratio of M to Si, and B is an atomic ratio of N to Si), and the thickness of the light-shielding film is set to 47 nm or less.
請求項10： Request item 10:
一種二元光罩坯料的製造方法，其係製造在透明基板上具備含有過渡金屬M及矽Si或過渡金屬M、矽Si及氮N作為主成分，且由單層或複數層構成之光學濃度3.0以上的遮光膜的二元光罩坯料之方法，其特徵為：將前述遮光膜形成為包含過渡金屬、矽及氮的組成滿足式(2)B≦1.19×A-0.19 (2) A method for producing a binary mask blank, which is provided with an optical density comprising a transition metal M and 矽Si or a transition metal M, 矽Si, and nitrogen N as main components on a transparent substrate, and consisting of a single layer or a plurality of layers A method of a binary mask blank of a light-shielding film of 3.0 or more, characterized in that the light-shielding film is formed to have a composition containing a transition metal, niobium and nitrogen to satisfy the formula (2) B ≦ 1.19 × A - 0.19 (2)
(式中，A為M相對於Si之原子比，B為N相對於Si之原子比)的層，將遮光膜的膜厚形成為43nm以下。 (wherein, A is a ratio of atomic ratio of M to Si, and B is an atomic ratio of N to Si), and the thickness of the light-shielding film is set to 43 nm or less.
請求項11： Request item 11:
一種二元光罩坯料的製造方法，其係製造在透明基板上具備含有過渡金屬M及矽Si或過渡金屬M、矽Si及氮N作為主成分，且由單層或複數層構成之光學濃度3.0以上的遮光膜的二元光罩坯料之方法，其特徵為：將前述遮光膜形成為包含過渡金屬、矽及氮的組成滿足式(3)B≦2.12×A-0.70 (3) A method for producing a binary mask blank, which is provided with an optical density comprising a transition metal M and 矽Si or a transition metal M, 矽Si, and nitrogen N as main components on a transparent substrate, and consisting of a single layer or a plurality of layers A method of a binary mask blank of a light-shielding film of 3.0 or more, characterized in that the light-shielding film is formed to have a composition containing a transition metal, niobium and nitrogen to satisfy the formula (3) B ≦ 2.12 × A - 0.70 (3)
(式中，A為M相對於Si之原子比，B為N相對於Si之原子比)的層，將遮光膜的膜厚形成為41nm以下。 (wherein, A is a ratio of atomic ratio of M to Si, and B is an atomic ratio of N to Si), and the thickness of the light-shielding film is set to 41 nm or less.
請求項12： Request item 12:
如請求項9至11中任一項之二元光罩坯料的製造方法，其中前述過渡金屬為鉬。 The method of producing a binary mask blank according to any one of claims 9 to 11, wherein the transition metal is molybdenum.
本發明之二元光罩坯料可充分遮蔽曝光時的光，且具備更薄的遮光膜，當對該二元光罩坯料進行光罩加工時，由於可使用更薄的阻劑膜，而能夠獲得高精度的二元光罩。又，只要對具有以本發明之鉻系材料等所形成之硬遮罩膜的二元光罩坯料進行光罩加工，即可獲得更高精度的二元光罩。 The binary mask blank of the present invention can sufficiently shield the light during exposure and has a thinner light shielding film, and when the mask processing is performed on the binary mask blank, a thinner resist film can be used, A high-precision binary mask is obtained. Further, as long as the mask cover having the hard mask film formed of the chromium-based material of the present invention or the like is subjected to mask processing, a binary mask of higher precision can be obtained.
1‧‧‧透明基板 1‧‧‧Transparent substrate
2‧‧‧遮光膜 2‧‧‧Shade film
21‧‧‧透明基板側的層 21‧‧‧layer on the transparent substrate side
22‧‧‧遠離透明基板之一側的層 22‧‧‧A layer away from one side of the transparent substrate
3‧‧‧蝕刻遮罩膜 3‧‧‧ etching mask film
第1圖為本發明之二元光罩坯料的第1態樣之一例的剖面圖。 Fig. 1 is a cross-sectional view showing an example of a first aspect of a binary mask blank of the present invention.
第2圖為本發明之二元光罩坯料的第2態樣之一例的剖面圖。 Fig. 2 is a cross-sectional view showing an example of a second aspect of the binary mask blank of the present invention.
第3圖為本發明之二元光罩坯料的第3態樣之一例的剖面圖。 Fig. 3 is a cross-sectional view showing an example of a third aspect of the binary mask blank of the present invention.
第4圖為本發明之二元光罩坯料的第4態樣之一例的剖面圖。 Fig. 4 is a cross-sectional view showing an example of a fourth aspect of the binary mask blank of the present invention.
第5圖為表示實驗例1中所得的膜之A值(過渡金屬M相對於矽Si之原子比)、B值(氮N相對於矽Si之原子比)及膜厚的圖。 Fig. 5 is a graph showing the A value (atomic ratio of transition metal M to 矽Si), B value (atomic ratio of nitrogen N to 矽Si), and film thickness of the film obtained in Experimental Example 1.
以下，對本發明更詳細地加以說明。 Hereinafter, the present invention will be described in more detail.
本發明之二元光罩坯料係作為由透光部與遮光部此2種部分所構成的二元光罩之素材者，在石英基板等的透明基板上，具有波長193nm下之光學濃度為3.0以上的遮光膜。在二元光罩中，去除掉遮光膜之僅有透明基板的部分屬透光部、於透明基板上存在有(殘留有)遮光膜的部分屬遮光部。該遮光膜由於是用於二元光罩，故光學濃度要求為3.0以上，較佳取3.5以下。就本發明之遮光膜，將膜厚作成47nm以下，尤為43nm以下，特別是41nm以下 時，仍可確保既定的遮光性。另一方面，遮光膜的膜厚的下限通常為10nm以上。 The binary mask blank of the present invention is a material of a binary mask composed of a light-transmitting portion and a light-shielding portion, and has an optical density of 3.0 at a wavelength of 193 nm on a transparent substrate such as a quartz substrate. The above light shielding film. In the binary mask, the portion where only the transparent substrate of the light-shielding film is removed is a light-transmitting portion, and the portion where the light-shielding film is left (remaining) on the transparent substrate is a light-shielding portion. Since the light shielding film is used for a binary mask, the optical density is required to be 3.0 or more, preferably 3.5 or less. The film thickness of the light-shielding film of the present invention is 47 nm or less, particularly 43 nm or less, particularly 41 nm or less. At the same time, the established opacity can still be ensured. On the other hand, the lower limit of the film thickness of the light shielding film is usually 10 nm or more.
本發明之二元光罩坯料係在透明基板上具有由單層或複數層(2層或3層以上)構成的遮光膜。作為具有由單層構成之遮光膜的二元光罩坯料，具體而言可舉出屬第1態樣之如第1圖所示，在透明基板1上形成有單層之遮光膜2者。另一方面，作為具有由複數層構成之遮光膜的二元光罩坯料，具體而言，例如為由2層構成的遮光膜時，則可舉出屬第2態樣之如第2圖所示，在透明基板1上，形成有由透明基板側的層21及遠離透明基板之一側的層22此2層所構成的遮光膜2者。 The binary mask blank of the present invention has a light-shielding film composed of a single layer or a plurality of layers (two layers or three or more layers) on a transparent substrate. Specific examples of the binary mask blank having a light-shielding film composed of a single layer include a single-layer light-shielding film 2 formed on the transparent substrate 1 as shown in Fig. 1 in the first aspect. On the other hand, the binary mask blank having a light-shielding film composed of a plurality of layers is, for example, a light-shielding film composed of two layers, and the second aspect is as shown in FIG. In the transparent substrate 1, a light-shielding film 2 composed of two layers of the layer 21 on the side of the transparent substrate and the layer 22 on the side of the transparent substrate is formed.
本發明之二元光罩坯料的遮光膜係含有過渡金屬M及矽Si或過渡金屬M、矽Si及氮N作為主成分。當遮光膜為單層時，該層需含有過渡金屬M及矽Si或過渡金屬M、矽Si及氮N作為主成分。另一方面，當遮光膜為複數層時，則至少1層需為含有過渡金屬M及矽Si或過渡金屬M、矽Si及氮N作為主成分的層(第1層)。該第1層的膜厚(該層有2層以上時為彼等之合計)較佳為遮光膜全體的膜厚的50%以上，尤以70%以上為佳。另一方面，其他的層(第2層)可為含有過渡金屬M及矽Si，並進一步含有由氮N、氧O及碳C中選出的1種以上者，惟較佳為所有的層為含有過渡金屬M、矽Si及氮N作為主成分的層。 The light-shielding film of the binary mask blank of the present invention contains transition metal M and 矽Si or transition metal M, 矽Si, and nitrogen N as main components. When the light shielding film is a single layer, the layer needs to contain transition metal M and 矽Si or transition metal M, 矽Si, and nitrogen N as main components. On the other hand, when the light shielding film is a plurality of layers, at least one layer needs to be a layer (first layer) containing the transition metal M and 矽Si or the transition metal M, 矽Si, and nitrogen N as main components. The film thickness of the first layer (the total of the layers in the case of two or more layers) is preferably 50% or more of the total thickness of the light-shielding film, and particularly preferably 70% or more. On the other hand, the other layer (the second layer) may contain the transition metal M and 矽Si, and further contain one or more selected from the group consisting of nitrogen N, oxygen O and carbon C, but it is preferred that all the layers be A layer containing a transition metal M, 矽Si, and nitrogen N as a main component.
當含有過渡金屬M及矽Si或含有過渡金屬 M、矽Si及氮N作為主成分的遮光膜以單層構成時，較佳含有合計80原子%以上的過渡金屬M、矽Si及氮N，較佳的是過渡金屬M為10原子%以上且35原子%以下，矽Si為50原子%以上且80原子%以下，氮N為0原子%以上，尤為1原子%以上且30原子%以下。又，當含有過渡金屬M及矽Si或過渡金屬M、矽Si及氮N作為主成分的遮光膜以複數層構成時，在含有前述過渡金屬M及矽Si或過渡金屬M、矽Si及氮N作為主成分的層(第1層)中，較佳含有合計80原子%以上的過渡金屬M、矽Si及氮N，較佳的是過渡金屬M為10原子%以上且35原子%以下，矽Si為50原子%以上且80原子%以下，氮N為0原子%以上，尤為1原子%以上且30原子%以下。另一方面，在前述其他的層(第2層)中，較佳含有合計35原子%以上的過渡金屬M及矽Si，較佳的是過渡金屬M為3原子%以上且35原子%以下，矽Si為30原子%以上且80原子%以下，氮N為0原子%以上，尤為10原子%以上且55原子%以下。在遮光膜及構成其之層中，亦可進一步含有氧O、碳C及此兩者作為輕元素成分，惟較佳為僅由過渡金屬M及矽Si、或過渡金屬M、矽Si及氮N構成。作為過渡元素，較合適者為鉬Mo。 When containing transition metal M and 矽Si or containing transition metals When the light-shielding film containing M, 矽Si, and nitrogen N as a main component is a single layer, it is preferable to contain a total of 80 atom% or more of the transition metal M, 矽Si, and nitrogen N, and preferably the transition metal M is 10 atom% or more. Further, 35 atom% or less, 矽Si is 50 atom% or more and 80 atom% or less, and nitrogen N is 0 atom% or more, and particularly preferably 1 atom% or more and 30 atom% or less. Further, when the light-shielding film containing the transition metal M and 矽Si or the transition metal M, 矽Si, and nitrogen N as a main component is composed of a plurality of layers, the transition metal M and 矽Si or transition metal M, 矽Si, and nitrogen are contained. In the layer (first layer) in which N is a main component, it is preferable to contain a total of 80 atom% or more of the transition metal M, 矽Si, and nitrogen N, and it is preferable that the transition metal M is 10 atom% or more and 35 atom% or less.矽Si is 50 atom% or more and 80 atom% or less, and nitrogen N is 0 atom% or more, and particularly preferably 1 atom% or more and 30 atom% or less. On the other hand, in the other layer (second layer), it is preferable to contain a total of 35 atom% or more of the transition metal M and 矽Si, and it is preferable that the transition metal M is 3 atom% or more and 35 atom% or less.矽Si is 30 atom% or more and 80 atom% or less, and nitrogen N is 0 atom% or more, and particularly 10 atom% or more and 55 atom% or less. The light-shielding film and the layer constituting the film may further contain oxygen O, carbon C, and both as light element components, but preferably only transition metal M and 矽Si, or transition metal M, 矽Si, and nitrogen. N constitutes. As a transition element, it is more suitable to be molybdenum Mo.
在含有過渡金屬M，尤為鉬Mo，及矽Si作為主成分的遮光膜、或含有過渡金屬M，尤為鉬Mo，及矽Si與氮N作為主成分的遮光膜中，藉由增加過渡金屬M的量，可提高每單位膜厚的光學濃度，而能夠減薄為了 獲得所需之光學濃度，即3.0以上之光學濃度所需要的膜厚。又，藉由減少氮N的量，可提高每單位膜厚的光學濃度，而能夠減薄為了獲得所需之光學濃度，即3.0以上之光學濃度所需要的膜厚。 In a light-shielding film containing a transition metal M, particularly molybdenum Mo, and yttrium Si as a main component, or a light-shielding film containing a transition metal M, particularly molybdenum Mo, and yttrium Si and nitrogen N as main components, by adding a transition metal M Amount that increases the optical density per unit film thickness and can be thinned for The desired optical concentration, i.e., the film thickness required for optical concentrations above 3.0, is obtained. Further, by reducing the amount of nitrogen N, the optical density per unit thickness can be increased, and the film thickness required to obtain a desired optical density, that is, an optical density of 3.0 or more can be reduced.
在本發明之二元光罩坯料中，當遮光膜為單層時、其層為複數層時，只要使構成該複數層的1層以上，較佳為所有的層之過渡金屬、矽及氮的組成滿足式(1)B≦0.68×A+0.23 (1) In the binary mask blank of the present invention, when the light shielding film is a single layer and the layer is a plurality of layers, as long as one or more layers constituting the plurality of layers are formed, it is preferable that all of the layers are transition metals, rhodium and nitrogen. The composition satisfies the formula (1) B ≦ 0.68 × A + 0.23 (1)
(式中，A為M相對於Si之原子比(M/Si，下同)，B為N相對於Si之原子比(N/Si，下同))，則可作成使遮光膜的膜厚(遮光膜全體的膜厚)成為47nm以下，且具有作為遮光膜所需之3.0以上之光學濃度的遮光膜。 (wherein, A is the atomic ratio of M to Si (M/Si, the same below), and B is the atomic ratio of N to Si (N/Si, the same below)), and the film thickness of the light-shielding film can be made. The film thickness of the entire light-shielding film is 47 nm or less, and has a light-shielding film having an optical density of 3.0 or more as a light-shielding film.
又，在本發明之二元光罩坯料中，當遮光膜為單層時、其層為複數層時，只要使構成該複數層的1層以上，較佳為所有的層之過渡金屬、矽及氮的組成滿足式(2)B≦1.19×A-0.19 (2) Further, in the binary mask blank of the present invention, when the light shielding film is a single layer and the layer is a plurality of layers, as long as one or more layers constituting the plurality of layers are formed, it is preferable that all of the layers are transition metals and ruthenium. And the composition of nitrogen satisfies the formula (2) B ≦ 1.19 × A - 0.19 (2)
(式中，A為M相對於Si之原子比，B為N相對於 Si之原子比)，則可作成使遮光膜的膜厚(遮光膜全體的膜厚)成為43nm以下，且具有作為遮光膜所需之3.0以上之光學濃度的遮光膜。 (wherein A is the atomic ratio of M to Si, and B is N relative to In the atomic ratio of Si, a light-shielding film having a film thickness of the light-shielding film (the film thickness of the entire light-shielding film) of 43 nm or less and an optical density of 3.0 or more required as a light-shielding film can be obtained.
再者，在本發明之二元光罩坯料中，當遮光膜為單層時、其層為複數層時，只要使構成該複數層的1層以上，較佳為所有的層之過渡金屬、矽及氮的組成滿足式(3)B≦2.12×A-0.70 (3) Further, in the binary mask blank of the present invention, when the light shielding film is a single layer and the layer is a plurality of layers, as long as one or more layers constituting the plurality of layers are formed, it is preferable that all of the layers are transition metals, The composition of niobium and nitrogen satisfies the formula (3)B≦2.12×A-0.70 (3)
(式中，A為M相對於Si之原子比，B為N相對於Si之原子比)，則可作成使遮光膜的膜厚(遮光膜全體的膜厚)成為41nm以下，且具有作為遮光膜所需之3.0以上之光學濃度的遮光膜。 (wherein, A is an atomic ratio of M to Si, and B is an atomic ratio of N to Si), and the film thickness of the light-shielding film (the film thickness of the entire light-shielding film) can be made 41 nm or less, and it can be used as a light-shielding. A light-shielding film of an optical density of 3.0 or more required for the film.
藉由使遮光膜所含之層的組成、及遮光膜的膜厚如此構成，即形成可確保作為遮光膜所需之遮光性，且具備更薄之遮光膜的二元光罩坯料，進而，藉由將前述式應用於遮光膜的構成元素之組成的設計，可配合膜厚有效地設定為了獲得更薄之遮光膜所需的構成元素，尤為過渡金屬、矽及氮的組成。若為前述式(1)~(3)任一者時，A的值較佳為0.1~0.6，尤為0.1~0.5的範圍，B的值較佳為0~0.5的範圍。又，在本發明中，亦能以複數 層構成遮光膜，並將其一部分作成具抗反射機能的層(抗反射層)。 By constituting the composition of the layer contained in the light-shielding film and the film thickness of the light-shielding film, a binary mask blank having a light-shielding property required as a light-shielding film and having a thinner light-shielding film can be formed, and further, By applying the above formula to the design of the constituent elements of the light-shielding film, it is possible to effectively set the constituent elements required for obtaining a thinner light-shielding film in combination with the film thickness, in particular, the composition of transition metal, cerium, and nitrogen. In the case of any of the above formulas (1) to (3), the value of A is preferably 0.1 to 0.6, particularly preferably 0.1 to 0.5, and the value of B is preferably in the range of 0 to 0.5. Also, in the present invention, it is also possible to The layer constitutes a light-shielding film, and a part thereof is made into a layer having an anti-reflection function (anti-reflection layer).
通常作為形成光罩坯料之遮光膜的手法，係採用反應性濺鍍等的濺鍍法，於本發明中亦較佳以濺鍍法來形成遮光膜。如欲調整形成之遮光膜及構成其之層的過渡金屬M相對於矽Si之比率(原子比)，若僅使用MSi混合靶時，可藉由改變靶的M/Si比來調整。又，以使用M靶與Si靶，調整成膜時對各者施加之電力的比例的方法，也可調整過渡金屬M相對於矽Si之比率。除此等之外，以使用2種以上之組成比不同的MSi靶的方法、或使用MSi靶與Si靶，調整成膜時對各者施加之電力的比例的方法，也可調整過渡金屬M相對於矽Si之比率。 Generally, as a method of forming a light-shielding film of a mask blank, a sputtering method such as reactive sputtering is used, and in the present invention, a light-shielding film is preferably formed by a sputtering method. To adjust the ratio (atomic ratio) of the formed light-shielding film and the layer constituting the light-shielding film to the 矽Si, if only the MSi mixed target is used, it can be adjusted by changing the M/Si ratio of the target. Further, the ratio of the transition metal M to the 矽Si can be adjusted by using the M target and the Si target to adjust the ratio of the electric power applied to each of the films. In addition to this, the transition metal M can also be adjusted by a method of using two or more MSi targets having different composition ratios, or by using a MSi target and a Si target, and adjusting the ratio of the electric power applied to each of the films at the time of film formation. Relative to the ratio of 矽Si.
另一方面，如欲調整形成之遮光膜及構成其之層的氮N相對於矽Si之比率(原子比)，一般而言，可藉由在成膜中導入N2氣體等含N的氣體而使遮光膜中含有N，並藉由調整成膜時導入的N量，可調整氮N相對於矽Si之比率。此外，使靶含有氮N，亦可調整氮N的量。濺鍍氣體中亦可添加Ar氣體等的惰性氣體。濺鍍壓力通常為0.02~0.5Pa。 On the other hand, in order to adjust the ratio (atomic ratio) of nitrogen N to 矽Si formed by the formed light-shielding film and the layer constituting the film, generally, an N-containing gas such as N 2 gas can be introduced into the film formation. Further, N is contained in the light-shielding film, and the ratio of nitrogen N to 矽Si can be adjusted by adjusting the amount of N introduced during film formation. Further, by making the target contain nitrogen N, the amount of nitrogen N can also be adjusted. An inert gas such as an Ar gas may be added to the sputtering gas. The sputtering pressure is usually 0.02 to 0.5 Pa.
就本發明之二元光罩坯料，亦可在遮光膜上形成有別於遮光膜的抗反射膜。作為此時的抗反射膜，較佳為增加N量的組成、或添加氧O來提升膜的透明性的組成者。又，就本發明之二元光罩坯料，也可在遮光膜上形成以對該遮光膜進行蝕刻時具蝕刻耐性之材料，即發揮 作為蝕刻遮罩之機能的材料所形成的硬遮罩膜。作為具有由單層構成之遮光膜的二元光罩坯料，具體而言可舉出屬第3態樣之如第3圖所示，在透明基板1上形成有單層之遮光膜2，並於其上進一步形成有蝕刻遮罩膜3者。另一方面，作為具有由複數層構成之遮光膜的二元光罩坯料，具體而言，例如為由2層構成的遮光膜時，則可舉出屬第4態樣之如第4圖所示，在透明基板1上形成有由透明基板側的層21及遠離透明基板之一側的層22此2層所構成的遮光膜2，並於其上進一步形成有蝕刻遮罩膜3者。 In the binary mask blank of the present invention, an antireflection film different from the light shielding film may be formed on the light shielding film. As the antireflection film at this time, it is preferable to increase the composition of N amount or to add oxygen O to improve the transparency of the film. Further, in the binary mask blank of the present invention, a material having etching resistance when the light-shielding film is etched may be formed on the light-shielding film, that is, A hard mask film formed as a material that etches the function of the mask. As a binary mask blank having a light-shielding film composed of a single layer, specifically, as shown in FIG. 3, a single-layer light-shielding film 2 is formed on the transparent substrate 1 and Further, an etch mask film 3 is formed thereon. On the other hand, as a binary mask blank having a light-shielding film composed of a plurality of layers, specifically, for example, a light-shielding film composed of two layers, a fourth aspect is as shown in FIG. The transparent substrate 1 is formed with a light shielding film 2 composed of a layer 21 on the side of the transparent substrate and a layer 22 on the side of the transparent substrate, and an etching mask 3 is further formed thereon.
尤其是當遮光膜的過渡金屬為鉬時，較佳為以鉻化合物形成的硬遮罩膜，該鉻化合物係含有一般用作硬遮罩材料的含鉻材料(鉻系材料)，例如鉻金屬、或鉻及由氧、氮及碳中選出的輕元素。 In particular, when the transition metal of the light-shielding film is molybdenum, a hard mask film formed of a chromium compound containing a chromium-containing material (chromium-based material) generally used as a hard mask material, such as chrome metal, is preferred. , or chromium and light elements selected from oxygen, nitrogen and carbon.
作為以鉻系材料形成的硬遮罩膜，可舉出日本特開2007-241060號公報(專利文獻3)所示者；惟，尤其是為了進行高精度的加工，硬遮罩膜本身亦需經過高精度加工。因此，硬遮罩膜的膜厚較佳為1nm以上且10nm以下。又，就硬遮罩膜的組成，較佳的是鉻為50原子%以上且100原子%以下，尤為60原子%以上且95原子%以下，氧為0原子%以上且50原子%以下，尤為0原子%以上且30原子%以下，氮為0原子%以上且50原子%以下，尤為5原子%以上且40原子%以下，碳為0原子%以上且20原子%以下，尤為0原子%以上且10原子%以下。 The hard mask film which is formed of a chrome-based material is as shown in JP-A-2007-241060 (Patent Document 3). However, in particular, in order to perform high-precision processing, the hard mask film itself is also required. After high precision machining. Therefore, the film thickness of the hard mask film is preferably 1 nm or more and 10 nm or less. Further, the composition of the hard mask film is preferably 50 atom% or more and 100 atom% or less, more preferably 60 atom% or more and 95 atom% or less, and oxygen is 0 atom% or more and 50 atom% or less, especially 0 atom% or more and 30 atom% or less, nitrogen is 0 atom% or more and 50 atom% or less, especially 5 atom% or more and 40 atom% or less, and carbon is 0 atom% or more and 20 atom% or less, especially 0 atom% or more. And 10 atom% or less.
硬遮罩膜的成膜較佳與遮光膜同樣地藉由濺鍍法來進行，可舉出例如使用鉻靶，僅以氬氣來進行的方法；在僅有氮或氮氧化物等反應性氣體、或者氮或氮氧化物等反應性氣體與氬氣等惰性氣體的混合氣體中進行反應性濺鍍的方法(例如參照日本特開平7-140635號公報(專利文獻4))。濺鍍氣體的流量只要配合膜特性來調整即可，於成膜中，可設為一定，而欲使氧量或氮量朝膜的厚度方向變化時，亦可配合目標組成來改變之。 The film formation of the hard mask film is preferably carried out by sputtering in the same manner as the light-shielding film, and examples thereof include a method of using only a argon gas using a chromium target, and a reactivity of only nitrogen or nitrogen oxides. A method of performing reactive sputtering in a gas or a mixed gas of a reactive gas such as nitrogen or nitrogen oxides and an inert gas such as argon gas (for example, see JP-A-7-140635 (Patent Document 4)). The flow rate of the sputtering gas may be adjusted in accordance with the film characteristics, and may be constant in the film formation. When the amount of oxygen or nitrogen is to be changed in the thickness direction of the film, the target composition may be changed.
本發明之二元光罩坯料特別適合作為ArF曝光(使用波長193nm之ArF準分子雷射光所進行的曝光)所使用的二元光罩用之二元光罩坯料。 The binary mask blank of the present invention is particularly suitable as a binary mask blank for a binary mask used for ArF exposure (exposure using ArF excimer laser light having a wavelength of 193 nm).
本發明之二元光罩坯料，可藉由在設於最表面的遮光膜、抗反射膜或硬遮罩膜任一者上形成阻劑膜，由該阻劑膜形成阻劑圖案，並以該阻劑圖案作為蝕刻遮罩圖案形成下層的膜的光罩圖案或蝕刻遮罩圖案，來製造二元光罩，惟，本發明之二元光罩坯料，在使用膜厚較薄的阻劑膜，例如150nm以下，尤為厚度50~120nm的阻劑膜時，仍可高精度地形成遮光膜圖案。 The binary mask blank of the present invention can form a resist film by forming a resist film on any one of a light shielding film, an antireflection film or a hard mask film provided on the outermost surface, and form a resist pattern from the resist film. The resist pattern is used as a mask pattern or an etch mask pattern for etching a mask pattern to form a lower layer film, but the binary mask blank of the present invention uses a thin film thickness resist. When the film is, for example, 150 nm or less, particularly a resist film having a thickness of 50 to 120 nm, the light shielding film pattern can be formed with high precision.
具體而言，如未形成硬遮罩膜時，可藉由：在二元光罩坯料的遮光膜上(形成有有別於遮光膜之抗反射膜時則在抗反射膜上)形成膜厚150nm以下之阻劑膜的步驟；形成阻劑膜之蝕刻遮罩圖案的步驟；使用阻劑膜之蝕刻遮罩圖案，在遮光膜上(形成有有別於遮光膜之抗反射膜時則在遮光膜及抗反射膜上)形成光罩圖案的步 驟；及去除阻劑膜之蝕刻遮罩圖案的步驟來製造二元光罩。 Specifically, when the hard mask film is not formed, the film thickness can be formed on the light shielding film of the binary mask blank (on the antireflection film when the antireflection film different from the light shielding film is formed) a step of forming a resist film of 150 nm or less; a step of forming an etching mask pattern of the resist film; and an etching mask pattern using a resist film on the light shielding film (when an antireflection film different from the light shielding film is formed) Step of forming a mask pattern on the light shielding film and the antireflection film And removing the etch mask pattern of the resist film to fabricate a binary mask.
另一方面，若形成有硬遮罩膜時，可藉由：在二元光罩坯料的硬遮罩膜上形成膜厚150nm以下之阻劑膜的步驟；形成阻劑膜之蝕刻遮罩圖案的步驟；使用阻劑膜之蝕刻遮罩圖案，對硬遮罩膜形成蝕刻遮罩圖案的步驟；使用硬遮罩膜之蝕刻遮罩圖案，對遮光膜(形成有有別於遮光膜之抗反射膜時則對遮光膜及抗反射膜)形成光罩圖案的步驟；及去除前述阻劑膜之蝕刻遮罩圖案及硬遮罩膜之蝕刻遮罩圖案的步驟來製造二元光罩。 On the other hand, when a hard mask film is formed, a step of forming a resist film having a thickness of 150 nm or less on a hard mask film of a binary mask blank; and an etching mask pattern for forming a resist film can be used. a step of forming an etched mask pattern on the hard mask film using the etch mask pattern of the resist film; etching the mask pattern using the hard mask film, and forming a mask different from the light-shielding film The step of forming a mask pattern on the light-shielding film and the anti-reflection film in the case of the reflective film; and the step of removing the etching mask pattern of the resist film and the etching mask pattern of the hard mask film to fabricate the binary mask.
以下示出實驗例、實施例及比較例來具體地說明本發明，惟本發明不受以下之實施例所限定。 The present invention will be specifically described below by way of Experimental Examples, Examples and Comparative Examples, but the present invention is not limited by the following examples.
在石英基板上，以濺鍍法，使用MoSi靶與Si靶，濺鍍氣體使用氬氣與氮氣，藉由變換對MoSi靶施加的電力、對Si靶施加的電力以及氬氣及氮氣的流量，而以光學濃度為3.0的膜厚形成組成不同的6種MoSiN膜，並藉由XPS(X射線光電子分光法)測定Mo、Si及N的組成。又，於各膜中，由所得之組成算出A值(過渡金屬M相對於矽Si之原子比)及B值(氮N相對於矽Si之原子比)，並利用A值算出相當於前述式(1)~(3)之右邊的值C1~C3 C1=0.68×A+0.23 C2=1.19×A-0.19 C3=2.12×A-0.70。將結果示於表1及第5圖。 On the quartz substrate, a MoSi target and a Si target were used by sputtering, and argon gas and nitrogen gas were used as the sputtering gas, and the electric power applied to the MoSi target, the electric power applied to the Si target, and the flow rates of argon gas and nitrogen gas were changed. On the other hand, six kinds of MoSiN films having different compositions were formed at a film thickness of 3.0, and the compositions of Mo, Si, and N were measured by XPS (X-ray photoelectron spectroscopy). Further, in each film, the A value (atomic ratio of transition metal M to 矽Si) and the B value (atomic ratio of nitrogen N to 矽Si) were calculated from the obtained composition, and the value corresponding to the above formula was calculated from the A value. (1)~(3) to the right of the value C1~C3 C1 = 0.68 × A + 0.23 C2 = 1.19 × A - 0.19 C3 = 2.12 × A - 0.70. The results are shown in Tables 1 and 5.
由此等結果可知，在以Mo、Si及N為主成分之光學濃度3.0以上的遮光膜中，可基於式(1)~(3)來設計使遮光膜成為既定的膜厚以下時可應用的組成。 According to the results, it is understood that the light-shielding film having an optical density of 3.0 or more containing Mo, Si, and N as a main component can be applied based on the formulas (1) to (3), and the light-shielding film can be applied to a predetermined film thickness or less. Composition.
在石英基板上，一面以於基板側，鉬為20原子%，矽為58原子%，氮為20原子%(此層於基板側的各值為A=0.34、B=0.34、C1=0.46)，於遠離基板的一側，鉬為22原子%、矽為62原子%、氮為15原子%(此層於遠離基板的一側的各值為A=0.35、B=0.24、C1=0.47)的方式使氮氣濃度連續地減少一面形成厚度43nm之屬組成傾斜層的MoSiN層。接著，以鉬為7原子%、矽為48原子%、氮為37原子%(此層的各值為A=0.15、B=0.77、 C1=0.33)的條件形成厚度4nm的MoSiN層，而形成由2層構成的遮光膜。 On the quartz substrate, on one side of the substrate, molybdenum is 20 atom%, yttrium is 58 atom%, and nitrogen is 20 atom% (the values of this layer on the substrate side are A=0.34, B=0.34, C1=0.46). On the side far from the substrate, molybdenum is 22 atom%, yttrium is 62 atom%, and nitrogen is 15 atom% (the values of this layer on the side far from the substrate are A=0.35, B=0.24, C1=0.47). In a manner, the concentration of nitrogen gas was continuously reduced to form a MoSiN layer of a composition layer having a thickness of 43 nm. Next, molybdenum is 7 atom%, 矽 is 48 atom%, and nitrogen is 37 atom% (the values of this layer are A=0.15, B=0.77, The condition of C1 = 0.33) forms a MoSiN layer having a thickness of 4 nm, and forms a light-shielding film composed of two layers.
所得遮光膜的膜厚為47nm，對波長193nm的光，光學濃度OD為3.05，來自基板側的光的反射率為34%，來自遠離基板之一側的光的反射率為32%。藉由在基板側形成含有滿足式(1)之過渡金屬M、矽Si及氮N的MSiN膜，可形成膜厚為47nm的遮光膜。 The film thickness of the obtained light-shielding film was 47 nm, the optical density OD was 3.05 for light having a wavelength of 193 nm, the reflectance of light from the substrate side was 34%, and the reflectance of light from one side away from the substrate was 32%. A light-shielding film having a film thickness of 47 nm can be formed by forming an MSiN film containing a transition metal M, 矽Si, and nitrogen N satisfying the formula (1) on the substrate side.
其次，以濺鍍法形成CrN膜〔Cr：N=9：1(原子比)〕使其膜厚成為10nm後，塗佈電子線曝光用阻劑而形成厚度150nm的阻劑膜，以電子束進行曝光，再進行顯像而形成阻劑膜之線寬為120nm的線與空間圖案(蝕刻遮罩圖案)。其次，藉由進行以Cl2氣體(185sccm)、O2氣體(55sccm)及He氣體(9.25sccm)為蝕刻氣體的乾式蝕刻，將CrN膜圖案化，轉印阻劑圖案而得到CrN膜之蝕刻遮罩圖案，其後，使用CrN膜之蝕刻遮罩圖案，進行以SF6氣體(18sccm)及O2氣體(45sccm)為蝕刻氣體的乾式蝕刻，以此對遮光膜進行乾式蝕刻，其後，去除阻劑膜之蝕刻遮罩圖案與CrN膜之蝕刻遮罩圖案，得到遮光膜的光罩圖案。 Next, a CrN film [Cr: N = 9:1 (atomic ratio)] was formed by sputtering to have a film thickness of 10 nm, and then a resist for electron beam exposure was applied to form a resist film having a thickness of 150 nm, and an electron beam was used. Exposure was carried out, and development was carried out to form a line and space pattern (etched mask pattern) having a line width of 120 nm of the resist film. Next, by performing dry etching using Cl 2 gas (185 sccm), O 2 gas (55 sccm), and He gas (9.25 sccm) as an etching gas, the CrN film is patterned, and the resist pattern is transferred to obtain a CrN film etching. After the mask pattern, the etching mask pattern of the CrN film is used, and dry etching using SF 6 gas (18 sccm) and O 2 gas (45 sccm) as an etching gas is performed, thereby dry etching the light shielding film, and thereafter, The etching mask pattern of the resist film and the etching mask pattern of the CrN film are removed to obtain a mask pattern of the light shielding film.
以SEM觀察所得遮光膜之光罩圖案的剖面形狀。由SEM的觀察，確認有垂直性良好的剖面。 The cross-sectional shape of the reticle pattern of the obtained light-shielding film was observed by SEM. From the observation by SEM, it was confirmed that there was a cross section with good perpendicularity.
在石英基板上，於基板側，以鉬為20原子%、矽為 70原子%且氮為6原子%(此層的各值為A=0.29、B=0.09、C2=0.15)的條件形成厚度39nm的MoSiN層。接著，以鉬為6原子%、矽為54原子%且氮為22原子%(此層的各值為A=0.11、B=0.41、C2=-0.06)的條件形成厚度4nm的MoSiN層，而形成由2層構成的遮光膜。 On the quartz substrate, on the substrate side, molybdenum is 20 atom%, and A MoSiN layer having a thickness of 39 nm was formed under the conditions of 70 at% and nitrogen at 6 at% (each of the layers was A = 0.29, B = 0.09, C2 = 0.15). Next, a MoSiN layer having a thickness of 4 nm was formed under the conditions of 6 atom% of molybdenum, 54 atom% of yttrium, and 22 atom% of nitrogen (each value of this layer was A=0.11, B=0.41, C2=-0.06). A light shielding film composed of two layers was formed.
所得遮光膜的膜厚為43nm，對波長193nm的光，光學濃度OD為3.00，來自基板側的光的反射率為51%，來自膜面側的光的反射率為45%。藉由在基板側形成含有滿足式(2)之過渡金屬M、矽Si及氮N的MSiN膜，可形成膜厚為43nm以下的遮光膜。 The film thickness of the obtained light-shielding film was 43 nm, the optical density OD was 3.00 for light having a wavelength of 193 nm, the reflectance of light from the substrate side was 51%, and the reflectance of light from the film surface side was 45%. By forming an MSiN film containing the transition metal M, 矽Si, and nitrogen N satisfying the formula (2) on the substrate side, a light-shielding film having a film thickness of 43 nm or less can be formed.
其次，以與實施例1同樣的方式得到遮光膜之光罩圖案，以SEM觀察其剖面形狀。由SEM的觀察，確認有垂直性良好的剖面。 Next, a mask pattern of a light-shielding film was obtained in the same manner as in Example 1, and the cross-sectional shape thereof was observed by SEM. From the observation by SEM, it was confirmed that there was a cross section with good perpendicularity.
在石英基板上，以鉬為33原子%、矽為65原子%且氮為2原子%(此層的各值為A=0.51、B=0.03、C3=0.38)的條件形成厚度40nm的MoSiN層，而形成由1層構成的遮光膜。 On the quartz substrate, a MoSiN layer having a thickness of 40 nm was formed under the conditions of 33 atom% of molybdenum, 65 atom% of yttrium, and 2 atom% of nitrogen (each value of this layer was A = 0.51, B = 0.03, C3 = 0.38). And a light shielding film composed of one layer was formed.
所得遮光膜的膜厚為40nm，對波長193nm的光，光學濃度OD為3.05，來自基板側的光的反射率為55%，來自膜面側的光的反射率為62%。藉由形成含有滿足式(3)之過渡金屬M、矽Si及氮N的MSiN膜，可形成膜厚為41nm以下的遮光膜。 The film thickness of the obtained light-shielding film was 40 nm, the optical density OD was 3.05 for light having a wavelength of 193 nm, the reflectance of light from the substrate side was 55%, and the reflectance of light from the film surface side was 62%. By forming an MSiN film containing the transition metal M, 矽Si, and nitrogen N satisfying the formula (3), a light-shielding film having a film thickness of 41 nm or less can be formed.
其次，以與實施例1同樣的方式得到遮光膜之光罩圖案，以SEM觀察其剖面形狀。由SEM的觀察，確認有垂直性良好的剖面。 Next, a mask pattern of a light-shielding film was obtained in the same manner as in Example 1, and the cross-sectional shape thereof was observed by SEM. From the observation by SEM, it was confirmed that there was a cross section with good perpendicularity.
在石英基板上，以鉬為17原子%、矽為55原子%、氮為28原子%(此層的各值為A=0.31、B=0.51、C1=0.44)的條件形成厚度48nm的MoSiN層，而形成由1層構成的遮光膜。 On the quartz substrate, a MoSiN layer having a thickness of 48 nm was formed under the conditions of 17 atom% of molybdenum, 55 atom% of yttrium, and 28 atom% of nitrogen (each layer has a value of A=0.31, B=0.51, C1=0.44). And a light shielding film composed of one layer was formed.
所得遮光膜的膜厚為48nm，對波長193nm的光，光學濃度OD為3.00，來自基板側的光的反射率為32%，來自膜面側的光的反射率為40%。於此MSiN膜情況下，若將膜厚減薄至低於48nm，則光學濃度未達3.0。對於含有不滿足式(1)之過渡金屬M、矽Si及氮N的MSiN膜，無法形成光學濃度為3.0以上，且膜厚為47nm以下的遮光膜。 The film thickness of the obtained light-shielding film was 48 nm, the optical density OD was 3.00 for light having a wavelength of 193 nm, the reflectance of light from the substrate side was 32%, and the reflectance of light from the film surface side was 40%. In the case of this MSiN film, if the film thickness is reduced to less than 48 nm, the optical density is less than 3.0. In the MSiN film containing the transition metal M, 矽Si, and nitrogen N which do not satisfy the formula (1), a light-shielding film having an optical density of 3.0 or more and a film thickness of 47 nm or less cannot be formed.
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